NanoSonic, Inc.

2017 Crosscutting Research Project ReviewAward #: DE‐SC0013811

Program Period: 8/1/16 ‐ 7/31/18Dr. Hang Ruan, Principal Investigator,  VP of Sensors and Systems

Dr. Yuhong (Echo) Kang, Nanoelectronics Lead ScientistDr. Richard Claus, Director of Advanced Development

NanoSonic, Inc.

TPOC Dr. Jessica Mullen

National Energy Technology Laboratory

March 23, 2017

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NanoSonic, Inc.

Program ObjectiveObjective: Develop wireless networked sensors using conformal nanomembrane based chemical field 

effect transistors (ChemFET) for heavy metal detection in water for energy sector. 

Electrostatic self‐assembly (ESA) + conformal nanomembrane ChemFET + wireless sensor network  in situ environmental monitoring

Key Expectations:o Heavy metal selectivity: RCRA 8s (arsenic, barium, cadmium, chromium, lead,  mercury, 

selenium and silver)o Heavy metal ion sensitivity: <0.01 ppm, with minimal cross‐sensitivitieso Sensor element size: <(100 micron)2o Dynamic range: >40dBo Frequency response: DC to >10kHzo Operating temperature: ‐40°C to 100°Co Multiplexing capability: >100 individual sensor elementso Power supply: Battery or integrated energy harvesting deviceo Transmission band: 2.4 GHz, IEEE 802.15.4 protocol; BLE protocolo Packaging options: Patch, Conformal, Portable, and Flowableo Operation mode: wake‐up, measurement, data transfer, and low‐power stand‐by

Nano‐CS Integrated RCRA 8 Sensor Probe

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1. Program Overview

2. Technical Results

3. Summary

Outline 

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How to Build a Wireless Sensor Network?

Sensing Unit  Processing Unit Transceiver Unit

Power Unit Location Finding System 

(optional)

Power Generator (optional)

Mobilizer (optional)

WSN Communication Architecture WSN Protocol Stack

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http://www.winstudent.com/wireless‐sensor‐networks/ Akyildiz et al., 2002

NanoSonic, Inc.5

Opportunity for Wireless Sensors for Heavy Metal Detection

Conventional chemical concentration sensing is typically done by taking soil or water samples on‐site and transporting them back to a laboratory for analysis, or hand‐carrying a sensor unit around an area and making, recording and mapping data.  

Multiple sensor devices can be configured in a small, lightweight and low cost array to analyze multiple sensor targets simultaneously. It can be used as an in‐situ sensor attachable for permanent installation or portable inspection in a field. 

To  allow  efficient  monitoring  of  heavy metal levels for environmental surveillance in water for fossil energy sector,   a   precise, mobile   and   highly   sensitive/selective/re‐usable   measuring instrument is required. 

Such systems can be used to• detect and map multiple environmentally‐hazardouschemical concentrations,• locate sources of pollution from analysis of concentration gradients, and• identify chemical concentrations potentially harmful to people and/or destructive to industry/agriculture.

UAV as a transceiver

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Advantages of NanoSonic’s Integrated Sensor Probes

For power plant operators and other customers, NanoSonic’s integrated sensor probes will  reduce total RCRA 8 water analysis costs,  reduce the number of hours of personnel field time required to obtain water samples,  reduce the time required to obtain water quality data back from analysis laboratories,  allow instantaneous alerts of significant increases in concentrations possibly indicative of unwanted events or 

failures,  permit the automated record‐keeping of historical water quality data, and  potentially reduce the likelihood and cost of remediation efforts and litigation related to high concentrations 

due to inadequate testing or overlooked pollution‐causing events.  

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Example of Potential Use ‐ Flue Gas Desulfurization (FGD) Wastewater Treatment

Potential use of RCRA 8 sensor to monitor the heavy metals  of treated effluent for real‐time close loop control

http://www.powermag.com/flue‐gas‐desulfurization‐wastewater‐treatment‐primer/

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Nanomembrane ChemFET Sensor Configuration

High Carrier Mobility    High Sensitivity High Selectivity

Ultralightweight Ultraflexibility Array  Configuration

Mask Design

‐2.00E‐07

‐1.00E‐07

0.00E+00

1.00E‐07

2.00E‐07

‐1 ‐0.5 0 0.5 1

Source

Drain

Current

(A)

Source Drain Voltage (Volts)

Source Drain I‐V Curve

‐2.00E‐07

‐1.00E‐07

0.00E+00

1.00E‐07

2.00E‐07

‐1 ‐0.5 0 0.5 1

Source

Drain

Current

(A)

Source Drain Voltage (Volts)

Source Drain I‐V Curve

I‐V characteristics of ChemFET

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Electrostatic Self‐Assembly

Conformal, homogeneous molecular layer by layer processPrecise nanoscale control over thickness

Excellent long‐term environmental robustness Environmentally‐friendly process

Multifunction – conductors, polymers, semiconductors, ceramics

Self Assembly Process:•polymer/polymer•polymer/particle•particle/particle

(ABAB)(ACAC)(ABAB)Multi-Segment

ABACABACABACABACMixed Property

ABACADAEAFAGAHAIFunctionally Graded 10‐5 cm

Metal Rubber™

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Silicon Nanomembrane

• Thin • Flexible• Can be strain engineered• Transparent• Transferable

• Bondable• Stackable• Conformable• Patternable (wires, 

ribbons, tubes)Nanomembrane–based ChemFET sensors

• 1974: Epitaxial Ga1‐xAlxAs (X>0.6) sacrificial layer for separating a GaAs/Ga1‐xAlxAs (x=0.3) from GaAs with HCl etchant • 1987: Yablonocitch: spin on wax to strain film for efficient release, enable removal of high quality GaAs films as large as 

0.8*2mm2 and as thin as 80nm• 2004: Rogers: transferred membranes of Si from silicon‐on‐insulator (SOI) to fabricate Si flexible thin‐film electronics• 2012: NanoSonic: Si nanomembrane based flexible solar cells• 2015: NanoSonic: Nanomembraned based ChemFET sensors

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Process Monitoring During Fabrication

I‐V characteristics of bulk and nanostructures with oxide mask and channel length of 5 µm, the sensor operates in the linear region 

Phosphorus doping profile at the channel‐drain side for bulk Si (left) and SOI nanomembranes (right) after source and drain doping. Oxide mask shown in dark red and buried oxide in SOI in dark red.

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NanoSonic, Inc.

Standard Sensor Packages

Standard Sensor Package Can be “Flowable” (Left), “Portable” (Center) and “Attachable” (Center Right) for Sensor Applications

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Self‐Assembly of Gold/Thiol Functionalization Layers

a) b)

c) d)

Exposed Channel Region

Source

Drain

Hand dipping (a, b) and Robot (c) Set Up Used to Self‐Assemble the Gold/Thiol Functionalization Layers. (d) Mircophotograph of a Completed Device with 9 Bilayers of Gold Nanoparticles in the 100 um by 100 um Channel Region. 

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Modification Example #1: Self‐Assembled Au and Thioglycolic Acid‐Functionalized ChemFET Sensor

Testing results of the self assembled Au and thioglycolic acid functionalized ChemFET sensor after exposure to different concentrations of (a) Hg, (b) Pb, (c) Cs, (d) Cr, and (e) As ion solutions, as well as (f) different targets with the same concentration of 10ppm. The 

response for the Hg ion is significantly higher than for other ions.

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Modification Example #2: : Sensor Modification for Lead Ion Selectivity

N,N,N′,N′‐Tetradodecyl‐3,6‐dioxaoctanedithioamide  Sodium tetrakis(4‐fluorophenyl)borate dihydrate

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NanoSonic, Inc.

Multi‐Target Selectivity Results for Self Assembled Au Sensor and Lead Ionophore Sensor

Cross sensitivity results with Bar Plot (a) and Radar Plot (b) for self assembled Au sensor and Lead ionophore sensor.

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NanoSonic, Inc.

Modification Example #3: Hybrid ESA/Au and ETH 5435 Functionalization

Time dependent response of the drain current for the hybrid ESA/Au and ETH 5435 functionalized ChemFET sensor. Noted that the responses for the Cr3+ and Cr6+, with the normalized current change of 2.9% for Cr3+ and 5.9% for Cr6+, are significantly higher than for other ions such as Cs, Cd, Hg, Pb and As. 

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Improvement #1: Self‐Assembled Graphene for Nanomembrane‐based ChemFET

Structure of Graphene Enhanced ChemFET (left) and Quasi‐1D nonequilibrium Green’s function Model (right)

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Graphene Precursors for Self Assembly 

NanoSonic, Inc.

‐0.8

‐0.6

‐0.4

‐0.2

0

0.2

0.4

0.6

0.8

1

1.2

1.4

Ag As Ba Cd Cr Hg Pb Se Normalized

Curen

t (%)

S28

S29

S32

S33

S41

‐0.6 ‐0.4 ‐0.2

0 0.2 0.4 0.6 0.8 1

1.2 1.4 Ag

As

Ba

Cd

Cr

Hg

Pb

Se

S28

S29

S32

S33

S41

Multiple sensor elements in an array can be used to simultaneously detect all RCRA 8 heavy metal targets.

Multiple Selective Functionalizations on Graphene Improved Sensors

‐1

‐0.5

0

0.5

1

1.5

2

0 20 40 60 80 100 120

Normalized

Drain

Current

(%)

Tes ng Time (Second)

O,O″‐Bis[2‐(methylthio)ethyl]‐tert‐butylcalix[4]arene Func onalized Gate

Ag

As

Ba

Cd

Cr

Hg

Pb

Se

S28 ‐ 0.01 ppm

‐1

‐0.5

0

0.5

1

1.5

2

0 20 40 60 80 100 120 Normalized

Drain

Current

(%)

Tes ng Time (Second)

N,N,N′,N′‐Tetrabutyl‐3,6‐dioxaoctanedi(thioamide) Func onalized Gate

Ag

As

Ba

Cd

Cr

Hg

Pb

Se

S29 ‐ 0.01 ppm

‐1

‐0.5

0

0.5

1

1.5

2

0 20 40 60 80 100 120

Normalized

Drain

Current

(%)

Tes ng Time (Second)

Calix[6]arene‐hexaace c acid hexaethylester Func onalized Gate

Ag

As

Ba

Cd

Cr

Hg

Pb

Se

S32 ‐ 0.01 ppm

‐1

‐0.5

0

0.5

1

1.5

2

0 20 40 60 80 100 120

Normalized

Drain

Current

(%)

Tes ng Time (Second)

1,10‐Dibenzyl‐1,10‐diaza‐18‐crown‐6, 7,16‐Dibenzyl‐1,4,10,13‐tetraoxa‐7,16‐diazacyclooctadecane, N,N′‐Dibenzyl‐4,13‐diaza‐18‐crown‐6 Func onalized Gate

Ag

As

Ba

Cd

Cr

Hg

Pb

Se

S33 ‐ 0.01 ppm

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NanoSonic, Inc.

Improvement #2: Stripping Voltammetry Enhanced ChemFETSensor

Self assembled Au/cysteine functionalized ChemFET sensor after exposure to different concentration of Ag ion solutions

Silicon Substrate (P+)

DGate Oxide

SSensing Materials

Silicon (P+)

BOX

‐ ‐ ‐ ‐ ‐ ‐ ‐

+ + + + + +

Heavy Metal Ions

R

Oxide

Encapsulation Encapsulation

20

‐0.0001

‐0.00005

0

0.00005

0.0001

0.00015

0.0002

0.00025

0 20 40 60 80 100 120

Source/drain

current (A)

Time (Second )

Chart Title

DI water0.01ppm Ag0.1ppm Ag1ppm Ag10ppm Ag

Ag Deposition

Ag Stripping‐0.0001

‐0.00005

0

0.00005

0.0001

0.00015

0.0002

0.00025

0 20 40 60 80 100 120

Source/drain

current (A)

Time (Second )

Chart Title

DI water0.01ppm Ag0.1ppm Ag1ppm Ag10ppm Ag

Ag Deposition

Ag Stripping

NanoSonic, Inc.

Wireless Sensor Modular Hardware

NanoSonic’s Wireless Sensor Modular Hardware, “M” Shape Antenna Operates at 2.4 GHz band with 25 Possible Channels 

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NanoSonic, Inc.

Tablet App to Read and Output Data

Low power tablet App with code to read, process and output the data wirelessly from the sensor to tablet.

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NanoSonic, Inc.23

Power Management of Wireless Sensor Network

Power‐Availability Duty Cycle Allows for Extremely Low Average Power Consumption for Wireless 

Sensor Nodes. 

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Demonstration of GPS Receiver to Determine Geographical Information

GPS hardware Raw GPS data taken at the NanoSonic facility

Google maps image showing the location of the received coordinates24

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DOE SOW vs. Progress Status

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Phase II Program Task

Quarter Projected Percent Complete

Actual Percent Complete 1 2 3 4 5 6 7 8

0 Kickoff mee ng with TPOC X 100% 100%

1 Develop improved understanding of sensor opera on through analysis and tes ng

X X X X 50% 60%

2 Further design polymer and semiconductor chemistries to improve sensor performance

X X X X 50% 60%

3 Develop means to compensate for cross‐sensi vity effects

X X X X X 20% 40%

4 Standardize sensor design and fabrica on X X X X 0% 20%

5 Develop simple means of sensor calibra on X X X X 0% 20%

6 Develop simple data acquisi on interface X X X 0% 20%

7 Use developed sensors through piggyback research tests with Phase II partners

X X X X X X 0% 20%

8 Field Test Nano‐CS RCRA 8 Sensor Probes at Steam‐Electric Power Plants and Other Sites

X X X X X X 0% 20%

9 Develop product transi on plan with the manufacture partner

X X X X X 0% 10%

NanoSonic, Inc.

NanoSonic has developed a sensor probe that selectively measures the concentrations of all eight RCRA heavy metals in water with sensitivities better than 0.01 ppm.

Data can be transmitted wirelessly with multi‐hop routing, or subsequently transmitted via the web.

Program Summary

Data refresh may be varied from seconds to days; rapid refresh means that emergencies can be detected.

NanoSonic is partnering with a water quality survey company, a major U.S. manufacturer of sensors and environmental controls, a regional Water Authority, and a major electric power company.

Phase II testing would be performed at regional power plants and other sites. 

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NanoSonic, Inc.

Acknowledgments

Thank YouDOE – Dr. Jessica Mullen and Dr. Bob Romanosky

andNanoSonic DOE SBIR Team

For Additional Information:

Hang RuanNanoSonic, Inc.

158 Wheatland Drive, Pembroke, VA 24136hruan@nanosonic.com

(540) 626‐6266

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